Manufacture of alcohols



Patented May 31, 1938 UNITED, STATES PATENT OFFICE.

2,1is,aa2 MANUFACTURE OF ALCOHOLS Alfred W. Francis, Woodbury, N. J., assignor to Socony-Vacuum ,Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing." Original application March 9, 1934, Serial No. 714,824. Divided and this application November 17, 1937, Serial No. 174,962

3 Claims.

'According to the processes known to the'art' at the present time, these alcohols are made by absorbing the proper oleflne in relatively concentrated sulfuric acid for the production of the corresponding alkyl sulfates. The mixture of alkyl sulfates and unreacted sulfuric acid is then diluted with considerable water in order to hydrolyze the alkyl sulfate to the corresponding alcohol, or alternately partially neutralized to bring about the same result, and the alcohol recovered from the resulting reaction mixture by aprocess of direct distillation. The major disadvantage of this prior art process is the consumption of sulfuric acid. In the formation of each mole of alcohol produced, at least one mole of sulfuric acid, and usually more than this amount, enters into the reaction. Upon the completion of the reaction, this mole of sulfuric acid reappears in a highly diluted or partially diluted and neutralized form. It cannot be reusedin the process without concentration and restoration if partially neutralized. The expense of such concentration and restoration may be greater than the cost of new acid, and will in most cases beof at least the same magnitude, so the process of the prior art may really be considered to consume at least one mole of sulfuricacid per mole of alcohol produced.

In addition, theknown process is one which requires two steps between the preparation of olefln'es and the distillation of alcohol from the reaction mixture, each with its difiiculties of control, each having its opportunitiesfor spoilage of product, loss of reagent, formation .of side products, and the like, and'each imposing its own peculiarities of reaction velocity, special conditions of operation, and completeness of reaction upon the overall eiflciency of the combined process.

It is a major object of this invention to overcome these difliculties by devising a process in which a single operating step suflices to pass from the olefine to the alcohol containing reaction product. A further object has been to devise a process of such direct hydratiqn'of olefines to alcohols capable of high yields and amenable to economic control. One of the principal objects is to devise a process wherein a minimum use of sulfuric acid is made per unit of alcohol produced,

and in which that sulfuric acid is regained from the reaction product in a condition which enables it to be used again in the process without expensive concentration and restoration. A further object has been the provision of a process capable of working upon an olefine raw material which is in the form of a liquid of a relatively high degree of purity. Further objects are the provision of a process whereby a product such as secondary butanol may be economically recovered from the reaction mixture in whichit originates without losses by decomposition, and such further objects and advantages as may hereinafter appear. 1 p

The process of the invention may be summarily described as one in which liquid olefines are heated under pressure in an autoclave whilst being agitated, in contact with dilute sulfuric acid or other equivalent strong, non-volatile mineral acid such as phosphoric acid. The efiiciency of the process is subject to the control of temperature, pressure, concentration of sulfuric acid, and other factors which are later discussed in more detail.

To explain, for an example of the process, the

manufacture of butanols, the oleflne raw material preferred for the process ,of this invention consists of substantially pure butenes, or a mixture of butene-l and butane-2, if the alcohol to be made is secondary butanol, or substantially pure isobutene, if the alcohol to be made is tertiary butanol. These oleflnes are introduced in a liquid or highly condensed form, and may be three moles of secondary butanol, or ten to twenty moles of tertiary butanol, per mole of sulfuric acid originally introduced to the reaction. A further characteristic is that this sulfuric acid is recovered, after distillation from the reaction mixture of the alcohol formed, in a condition such that it may be returned directly to the primary reaction. What this amounts to from aneconomic standpoint is that the consumption of acid in the process is in reality zero, except for leakage, spills, and mechanical and other losses of like nature.

-. made as follows.

A broad statement of the operating characteristics of the process of the invention may be The temperature of the reaction is that temperature at which the rate of reaction is found to be favorable. The preferred place to an objectionable extent with stronger acid. It is preferred that the relative amounts of ,oleflne and water be such that the water is slightly in excess. For example, the preferred. amount is one such that the water present is about 20 per cent to 30 per cent in excess of that amount equivalent to the oleflne present. This slight excess of water is.desirable to avoid side reactions, as for instance, excessive formation of til-secondary butyl ether when the desired product is secondary butanol. Agitation of the reaction mixture is necessary, as the system tends tofpart into twoliquid layers.

In the manufacture of secondary butanol, the starting material is butene-l or butene-2, or a mixture'of these in substantially pure condition in the form of a liquid. The concentration of sulfuric acid preferred is 60 to 65 per cent, as polymerizationof the olefine is likely to occur with acids stronger than 65%. The relative amounts 'of reagents are such that water is present to the extent of 20 to 30 per cent in excess of the'oleiine, as pointed out above. The reaction temperature preferred is 60 to 70 C, Lower temperatures can be used, but the rate of reaction becomes uneconomically slow with much decrease in temperature. 0n the other hand, 70 C.- is the preferable upper limit for the reaction temperature for the formation of secondary butanol. At higher temperatures the equilibrium corresponds to only 30 to 40 per cent hydration, and results in a two phase liquid product so that only low yields may be expected. At temperatures slightly lower than 70 C., enough alcohol is formed to'produce. a homogeneous reaction mixture so that hydration proceeds to or per cent of completion.

The temperature which distinguishes between these two alternate results. varies slightly with the concentration. of the sulfuric acid and the, purity of the olefine, but with a given pair of reagents is very sharp, a difference of one degree allowing more than double the yield in one case than in the other.

The preferred pressure held upon the reaction mixture issubstantially equal to or in excess of the vapor pressure of the'olefine at the reaction temperature. when operating with butenes at a temperature of 70 0., it is preferably about 115 pounds per square inch gauge.

Under the preferred conditions outlined, the reaction is practically complete after about three hours. When complete, the reaction mixture may then be distilled directly to reco'ver'the alcohol formed, but minimum losses of alcohol occasioned by reversal of synthesis during distillasomewhat with water. The amount of water is preferably substantially equal to that consumed in the hydration plus that to be withdrawn with the alcohol as a, constant boiling mixture in the following distillation. The reason for this preferred'dilution is t'p place the distillation residue at a concentration which will permit immediate return to the synthesis step.

.The alcohol. is then distilled from the reaction mixture. This distillation is carried out by heating the mixture to some temperature, for example, 70 C., considerably below its boiling point,

and passing a gas through it. The preferred gasv for this use is the same olefine which has been used in synthesizing the alcohol, since this aids in suppressing decomposition. This suppression of decomposition is the reason for the reduced temperature of distillation, since at the boiling point of the mixture, about C. at atmospheric pressure, there would be a serious loss of alcohol by reversal of its synthesis. In this connection, the term boiling point is intended to mean that temperature at which there is substantial evolution of a gaseous phase, regardless of its nature or origin. An inertgas, or vacuum distillation also may be used, but these methods are much less eificlent as a means of avoiding decomposition.

The condensed collected distillate will consist usually of two liquid layers. The upper or alco- -hol layer may be separated, and, if desired, dried by any of the usual methods known to the art, as for example by use of salt, caustic soda, etc. The residue from the distillation consists of sulfuric acid,suitable in purity and concentration for di rect return form in another hydration reaction. For the manufacture of tertiary butanol, the starting olefine is isobutene. In this case; the much greater reactivity of isobutene permits the use of a more dilute sulfuric acid, a strength of 5 to 10 per cent being satisfactory, though as little as 0.5 per cent may give a useful result. In

this case, the maximum temperature for a homogeneous reaction mixture at equilibrium is about 90. 0.), issufllciently below the reaction temperature to avoid decomposition.

In this case, the condensed and collected distillate presents a single phase, and contains about 87 per cent tertiary butanol by weight. This product can likewise be dried by any of the usual methods, it it is desirable.

In the disclosure of this invention herein set forth and particularly in the explanatory matter, the statements of temperatures, pressures, concentrations, reagents used and other data are givenv in an exemplary manner only, and it is not intended that the invention belimited thereby, but only by such limitations as may appear in the appended claims.

'This application is a division of my co-pending application, Serial No. 114.824, filed March 9,

f 1934. tion may be had if'the reaction mixture is diluted What is claimed is: 1. In the process for the preparation of tertiary butanol from isobutene, the steps which comprise bringing isobutene into intimate contact with sulfuric acid of a strength not greater than 65 per cent, and in the absencepf other catalytic material, heating the mixture to a temperature not 2,1 races in excess of 120 C., under an elevated pressure of -isobutene the steps which comprise bringing the butene into intimate contact with a solution containing a strong non-volatile mineral acid and water, heating the mixture thus obtained under elevated pressure whilst agitating it, the temperature oi the mixture being below that temperaat; and

ture at which insuflcient alcohol is formed by reversal of the synthesis to produce a homogeneous reaction mixture at equilibrium and the concentration of the 'acid being not greater than about 65%, and the pressure upon the mixture being sumcient to keep the butene of a density at Patent No. 2,118,882

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page-5 second line 12, claim 5', for "raction mixture of" read reaction mixture that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent column,

Office.

Signed. and sealed this ll th day of March, A.D. 19 59.

isel) ALFRED w. FRANCIS.

least approximating that of the butene in a liquid condition.

3. In the manufacture of tertiary butanol from isobutene the steps which comprise bringing the butene into intimate contact with a solution con- 5 taining a strong non-volatile mineral acid and water, heating the mixture thus obtained under elevated pressure whilst agitating it, the temperature oi the mixture being below that temperature at which insufiicient alcohol is formed by 10 I reversal of the synthesis to produce a homogeneous raction mixture of equilibrium and the concentration of the acid being not greater than about 10% and not less than about 0.5%, and the pressure upon the mixture being sufficient to keep 5 the butene of a density at least approximating that of the butene in a liquid condition.

ALFRED w. FRANCIS:

Henry Van Arsdale Y Acting Commissioner of Patents.

2,1 races in excess of 120 C., under an elevated pressure of -isobutene the steps which comprise bringing the butene into intimate contact with a solution containing a strong non-volatile mineral acid and water, heating the mixture thus obtained under elevated pressure whilst agitating it, the temperature oi the mixture being below that temperaat; and

ture at which insuflcient alcohol is formed by reversal of the synthesis to produce a homogeneous reaction mixture at equilibrium and the concentration of the 'acid being not greater than about 65%, and the pressure upon the mixture being sumcient to keep the butene of a density at Patent No. 2,118,882

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page-5 second line 12, claim 5', for "raction mixture of" read reaction mixture that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent column,

Office.

Signed. and sealed this ll th day of March, A.D. 19 59.

isel) ALFRED w. FRANCIS.

least approximating that of the butene in a liquid condition.

3. In the manufacture of tertiary butanol from isobutene the steps which comprise bringing the butene into intimate contact with a solution con- 5 taining a strong non-volatile mineral acid and water, heating the mixture thus obtained under elevated pressure whilst agitating it, the temperature oi the mixture being below that temperature at which insufiicient alcohol is formed by 10 I reversal of the synthesis to produce a homogeneous raction mixture of equilibrium and the concentration of the acid being not greater than about 10% and not less than about 0.5%, and the pressure upon the mixture being sufficient to keep 5 the butene of a density at least approximating that of the butene in a liquid condition.

ALFRED w. FRANCIS:

Henry Van Arsdale Y Acting Commissioner of Patents. 

